Photographic supersensitizing combinations comprising aminocarbocyanine dyes



United States Patent O PHOTOGRAPHIC SUPERSENSITIZING COMBINA- TIONS COMPRISING AMINOCARBOCYANINE DYES Jean E. Jones, Rochester, N. Y., assigner to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application July 20, 1954, Serial No. 444,546

20 Claims. (Cl. 95-7) This invention relates to photographic emulsions containing cyanine (e. g., carbocyaniue) dyes containing a meso amino group, and in supersensitizing combination, certain un-ionized dyes.

lt is known in the art of making photographic emulsions that certain dyes of the cyanine class alter the sensitivity of photographic emulsions of the gelatinosilver-halide kind, when the dyes are incorporated in the emulsions. -It is also known that the sensitization produced by a given dye varies somewhat with the type of emulsion in which the dye is incorporated. Furthermore, the sensitization of a given emulsion by a given dye may be altered by varying the conditions in the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e. increasing the alkalinity) or both. Thus, sensitization can be increased by bathing plates, coated with a spectrally sensitized emulsion, in water or in aqueous solutions of ammonia. Such a process of altering the sensitivity of a sensitized 'emulsion by increasing the silver ion concentration and/or by decreasing the hydrogen ion concentration is commonly called hypersensitization Hypersensitized emulsions have generally poor keeping qualities.

I have now found an improved means of altering the sensitivity in emulsions containing cyanine dyes. Since the conditions in the emulsion, i. e. the hydrogen ion and/or the silver ion concentration undergo little or no change in my method, I shall designate my method as a kind of supersensitization.

It is, therefore, an object of my invention to provide photographic emulsions containing cyanine dyes, ,and in supcrsensitizing combination therewith, certain un-ionized dyes. Another object is to provide a process for preparing these supersensitized emulsions. Other objects will become apparent from a consideration of the following description and examples.

The carbocyanine dyes containing a meso amino group useful in practicing my invention can advantageously be represented by the following general formula:

resents a hydrogen atom, an alkyl group, such as methyl, p

ethyl, n-propyl, isopropyl, n-amyl, n-heptyl, n-octyl, etc., an aromatic group, such as phenyl, o, m, and p-tolyl, p-dimethylaminophenyl, a-naphthyl, -naphthyl, o, m, and p-chlorophenyl, o,V m, and p-methoxyphenyl, 0,

m, and p-ethoxyphenyl, etc., a hydroxyl group (Ro is l hydrogen), or an arylhydrazino group, such as phenylhydraziuo, p-tolylhydrazino, p-methoxyphenylhydrazino, etc. or Ru and Rz together represent a piperidyl or morpholinyl group, X represents an acid radical, such as chloride, bromide, iodide, perchlorate, thiocyanate, t

2,704,719 Patented Mar. 22, 1955 ice benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, etc., and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiazole series, such as benzothiazole, S-methylbenzothiazole, 5-ethy1- benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, -methylbenzothiazole, -ethylbenzothiazole, 6- chlorobenzothiazole, 6bromobenzothiazole, S-methoxybenzothiazole, S-ethoxybenzothiazole, 6-methoxybenzothiazole, -ethoxybenzothiazole, 5-phenylbenzothiazole, -phenylbenzothiazole, S-aminobenzothiazole, 6-aminobenzothiazole, 5-dimethylaminobenzothiazole, etc., and those of the naphthothiazole series, such as anaphthothiazole, -naphthothiazole, etc. For purposes of convenience, the group in the above formula can be designated simply R', wherein R is an amino group (substituted or unsubstituted).

'l'he un-ionized dyes useful in practicing my invention can advantageously be represented by the following general formula:

---iJ-oe wherein R3 and R4 each represents an alkyl group, i. e. an alcohol radical, e. g., methyl, ethyl, n-propyl, n-butyl, /S-hyoroxyethyl, caroethoxymethyl, benzyl (phenylmetuyl), etc., Q represents the non-metallic atoms necessary to complete an indandione nucleus or a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as those ot' the pyrazolone series (e. g., 3- metuyl-l-phenyl-j-pyrazolone, l-phenyl-S-pyrazolone, 1- (2-benzothiazoiyl3-methyl5pyrazolone, etc.), those of the isoxazolone series (e. g., 3-phenyl-5-(4rU-isoxazolone, 3methyl5(4il)isoxazolone, etc.), those of the indandione series (e. g., l,3-diketohydrindene, etc.), those ot the oxndole series (e. g., l-alkyl-2,3dihydro- 2-oxinuoles, etc.), those of the 2,4,6-tr1ketonexahyoropyrimidine series (e. g., barbituric acid or Z-thiobarbituric acid, as well as their l-alkyl (e. g. l-methyl,` 1ethyl, l-n-heptyl, etc.), or l,3dialkyl (e. g., 1,3-dimethyl, 1,3- diethyl, l,3dinpropyl, 1,3-diisopropyl, 1,3-dicyclohexyl, 1,3-di(methoxyethyl), etc.), or 1,3-diaryl (e. g., 1,3-diphenyl, l,3di(pchlorophenyl), l,3-di(pethoxy carbonylphenyl), etc.), or l-aryl (e. g., l-phenyl, 1-pchlorophenyl, l-p-ethoxycarbonylphenyl, etc.) or 1- alkyl-I-aryl (e. g., l-ethyl-3-phenyl, 1nheptyl3pheny1, etc.) derivatives), those of the rhodanine series (i. e. Z-thio-ZA-thiazolidinedione series) such as rhodanine, 3alkylrhodauines (e. g., 3-ethylrhodanine, 3-allylrhodanine, etc.) or 3-arylrhodanines (e. g., 3phenylrhodanine, etc.), etc., those of the imidazo L1,2a]pyridin2(3ll) one series, those of the 5,7-dioXo-,7-dihydro-5-thiazole [3,2-alpyrimidine series (e.'g., 5,7-dioxo-3-phenyl-6,7- dihydro-S-thiazole[3,2-alpyrimidine, etc.), those of the 2-thio-2,4oxazolidinedione series (i. e., those of the 2-thio-2,4(3H, 5H)oxazoledione series) (e. g., '3a-ethyl- 2-thio-2,4oxazolidinedione, etc.), those of the thianaphthenone series (e. g., 2(3H)thiauaphthenone, etc.), those of the 2-thio-2,5thiazolidinedione series (i. e. the 2-thio2,5 (3H, 4H)thiazoledione series) (e. g., 3-ethyl-Z-thio-2,5thiazolidinedione, etc.), Zz represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, e. g., a heterocyclic nucleus of the benzothiazole series (e. g., benzothiazole, 4chloro benzothiazole, S-chlorobenzothiazole, -chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5- methylbenzothiazole, -methylbenzothiazole, 5-bromobenzothiazole, -bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothazole, 5-methoxybenzothiazole, -methoxybenzothiazole, 6-iodobenzothiazole, 5-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, 5,6dimethoxya-na'phtho'xazole -naphthoxazole, etc.), etc. and lZ3 rep- Y resents the non-metallic atoms'necessary to complete "a Vheterocyclic nucleus of thev naphthothiazole series( such as those listed above for Z2) or the naphthose'lenazole 4series (such as those listed l'above for Z2).

' `Dyesof Formula II above which have been found to be particularly useful in practicing my invention include dyes selectedV from Vthose represented by the following general formula: III S --Rt @Y wherein R`3,"R4, Z3 and Q each` have the values given above. Particularly useful are those dyes wherein Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the barbituric acid series and fZaerepresentsthe vnon-metallic atoms necessary to comple'te a heterocyclic nucleus of the naphthothiazole series `o1" :the naphthoselenazole series.

I I have also found that dyes lselected from those .representedbyFormula Irabove wherein Ro is an alkyl group,

i such as methyl, ethyl, etc. (e. g., an alkyl group of the "formula'CaIfIzahriV wherein d represents a positive integer joffroml -to..2). audRz represents a mononuclear aromatic group of Athe benzene series, such yas phenyl, v0-, m-Yand p-tolyl, etc-can be advantageously employed in -practicing my invention. l f -'IThe-'dyesrepresented Vby Formula I -above Vcan be `prepared as describedin the'copending Aapplication Serial No..437,1l0, led June 16, 1954, of Leslie G. S. Brooker and-F.L.YWhite.rf (The dyes-of 'Formula II (or III) are described inthe copending applications Serial No. 282,696-, led April V16, .1952, now abandoned, and SerialNo. 375,279, led .August 19, 1- 1953, of F. L. White and Leslie G.'S. -Brooken Y Y According-.to my invention, I incorporate one or more of the cyanine Adyes selected 4from those represented by Formula I vabove with one 0rI more ofsthe dyes selected -from those represented by Formulas II or'III above-in a photographic emulsion. My inventionis particularly Ydirected to the ordinarily employed gelatino-silver-halide emulsions. However, fmy supersensitizing combinationsV -canbe employed `1n silver'rhalide -emulslons -1n whichV The optimum lconcentration of my supersensitizing com; 'binations can, of course, be readily determined in the same manner, by measuring the sensitivity of a series of test portions of the'same emulsion, each portion containing different concentrations of the individual dyes in the combination. In determining the optimum concentration for the supersensitizing combination, itj is advantageous to employ, at first, concentrations ofthe individual dyes less than their optimum concentrations.

The concentrations of the individual dyes canthen be increased until the optimum concentration of the supersensitizing combination is determined.

Ordinarily the optimum or near optimum concentra tion ofV the cyanine (i.V e. carbocyanine) dyes selected from those-represented by Formula I above, which I employ in practicing my invention, is of the order of from 0.05 to 0.3 g. pery mol. of silver halide in the emulsion.V

The un-ionized dyesV selected from those represented by Formula II (or III) above areadvantageously fem- VployedY in concentrations on the 'order of -from .Ol to 0.3 g. per mol. ofV silver halidejn the emulsion. i

Generally `speak-ingjtheratio of'i'concentration of the dye of Formula II or IIIk to the cyanine dye of 'Formula VI can vary rather widely in my combinations, e.` g. `from 1:20 to 3:1'byweight in many cases. Y

The methods of incorporating sensitizing dyes in emulsions are well known tothose skilled in the art. In practicing my invention, thesensitizing dyes can be incorporated in the emulsions separately or`together. AIt is convenient to add Athe dyes separately in the form of solutions in appropriate solvents; MethanoL ethanol, pyridine, etc. and especially pyridine) have proven satisfactory as'solvents forthe'dyes of Formulasl, II, III vwhich I employ. Acetone 'has yalso been found to 'be a suitable solvent in certain cases." 'In general, it is advantageous to vemploy pyridine, diluted withmethanol or acetone, as the solventfor thesupersensitizing combinations of my invention.-v For example, the dye can `be dissolved in pyridine and the solution then diluted with methanol or acetone. The' dyesar'e advantageously incorporated in the iinished,' washed Vemulsions and should be uniformly distributed throughout the emulsions.Y The following procedure is satisfactory; Stock solutions of the sensitizing dyes desired are prepared by Y dissolving the Vdyes in appropriate solvents as described above. Them' to the owa'bleg gelatino-silve'r-halide emulsion, the desired amounts of Vthe stock solution of one of the dyes are slowly added, while stirring the jemulsion. Stirring isV continuedV until .thoroughly incorporated Vin the emulsion. Then the .de-

sired amount of the stock solution of the second dye is slowly added to the emulsion, whilestirring. Stirring Vis continued until the secondrdye'is .thoroughly incorporated. The supersensitized emulsion' can then be coated out on a suitable support, such as glass', .cellulose y dye to dye, according to the emulsion employed and Vthe lcarrierris 'other than gelatin, er `g.-,-aresinous sub- 4stance or.cellulosic material -which Vhas 'no Vdeteriorating eiect onv the light-sensitive-materials.A :The sensitizing dyes can #be employedin various con- `centrationsdepending upon. the veffects desired. As is -well :known in the art, the Vsensitivityconferred-,upon ,Y

Iansemulsion by a sensitizing dye does not increase Vproportionately to the concentration of the Vdye .in the emulsion, huttrather passes through a maximum as the vconcentration isincreased. Inpracticing my invention, the individual sensitizing dyes'are advantageously `employed .in ra concentration somewhat less than their optimum Aconcentration (iQe. the concentration at which the individual dyes givergreatest sensitivity). If each ofthe Vdyes .in the supersensitizing combination is employed-'in lits optimum concentration, it is possible, incertain cases Ythat `the `sensitization produced by the supersensitizing -combination willhave passed through a maximum.

The optimumconcentration of an individual sensitizing .dyecaniberdetermined in a manner well known to those skilled in the art by measuring .the sensitivity of a series Voi-test portions of the vsame emulsion, leach portion .con-

Ytaining a dilerent concentration of the senstizing dye.

according to the elect desired. The regulation and adoption of the most economical and usefulV proportions 1 will be apparent to those skilled .in the Vart uponnmaking the ordinary observations and tests ycustomarily employed in the/art. Accordingly, the 'foregoingfprocedures'and proportions are to be regarded` onlyfas illustrative. 'Clearly my invention 'is directed tol'any emulsion containing a combinationof the aforesaid sensitizing dyes whereby a supersensitizing effect is obtained. Y

VThe following examples Vwill serve tio-illustrate further the manner of practicing niy invention.V To different portions `of the Vsame batch ofV photographic gelatinesilver-bromiodde emulsion were added (l) a cyanine dye selected lfrom those of VFormula I and (2') a conrbination of the cyanine dye of, Formula I and Van' un- -onized dye selected from'those represented Yby Formula II (or III) above. was prepared using the lsame emulsionrformula and a single dye,V one ofthe uil-ionized dyes selected from those of Formula II `(or III). In ysome instances, the

table will show thatthisthird coating gave Yonly alow.

In Asome instances, a Y'third coating,

Dierent emulsions were used in some of the examples, although the emulsions of each individual example were obtained from rthe same batch. However, the coatings of Examples 1-4 were obtained from the saine batch of emulsion, the coatings of Examples 5-15 were obtained from the same batch, the coatings of Examples 16-21 were obtained from the same batch, and the coatings of Examples 22 and 23 were obtained from the same batch of emulsion. Before coating, the emulsions were digested for a short time in a tank maintained at: 52 C. The diierent portions of emulsions were then coated on supports and exposed in the usual manner in a spectrograph and a sensitometer (Type Ib) through a Wratten No. 25 lter, i. e., a lter which transmits substantially no light of Wavelength shorter than 580 mu. (See Kodak Wratten Filters for Scientific and Technical Use, Eighteenth edition, page 31). The red speed, gamma, and fog were then determined after conventional .6 Figures -l and 2 the sensitivity conferred on the emulsionby the un-'ionized dye of Formula II (or III) alone has been omitted, since none could be detected under the conditions employed. In Figure 3 the sensitivity conterred on the emulsion by the cyanine dye of Formula I is not represented, since it would correspond essentially to curve A in Figure l.

In Figure 1 curve A represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3' dimethyl 9 N methylanilino 4,5,4',5 dibenzothiacarbocyanine iodide and curve B represents the sensitivity of the same emulsion containing 3,3' di methyl 9 N methylanilino 4,5,4,5 dibenzothia carbocyanine iodide and 5 [di(l ethyl 2(1H) naphthothiazolylidene)isopropylidenel 1,3 d( methoxyethyDbarbituric acid. The sensitometric measurements for these emulsions are given in Example 9 of the above table.

The coatings in Examples 1 to 4 of the above table contained cc. of pyridine per mole of silver halide. The accompanying drawing illustrates the supersensitizing effect obtained with three of my new combinadevelopment. The results are recorded in the following In Figure 2. curve C represents the sensitivity of an table. ordinary gelatino-silver-bromiodide emulsion sensitized .J Red Light Exposure Ex. Dye (e/nwle AsX) Sagg'd Gamma Fog (a) 9-Ani1ino-3,3dmethylthiacarboeyanine ptoluenesulfonate (0.080) 12.5 2.9 .05 1 (b) 1,3-ditgiyl-[di(1-ethy1-2(1H)--naphthothiazolylidene)isopropylidene] barbituric 28. 5 1. 6 .08

aci 0.02

(c) dye (u) (0.080) with dye (b) (0.020) 35.0 2.6 .06 (d) 9-ecetanilido-3,3dimethylthiacarbocyanine p-toluenesulfonate (0.080) 5. 7 1.8 .06 2 ((e) dye (d) (0.080) with dye (b) (0.020) 38.0 2.5 .04 3 {(f) Q-(acetyl p-phenetidino)-3,3dimethylthiacarbocyanine p-toluenesulfonete (0.080) 14.7 2. 5 .05 1(9) dye (f) (0.080) with dye (b) (0.020) 50.0 2. 5 .07 (h) 9(pdin3iethylaminoacetanilido)3,3dimethylthiacarbocyanine p-toluenesulfonate 2.85 .85 .08 4 (0.080

j[() dye (h) (0.080) with dye (i) (0.020). 34. 5 2. 3 .08 (j) 3,3-dimethyl-9-p-phenetid1no4,5,4',5dibenzothiacarbocyanine chloride (0.080) 27. 5 2. 4 .08 (It) 5-[di(1-ethy1-2(1H)--naphthothiazolylidene)isopropylidene]1,3di(B-methoxyethyl) 5 barbiturie acid (0.080).

(Z) dye (j) (0.080) with dye (k) (0.030) 58.5 2.0 .06 6 f('m) 3,3diethy19(2-phenylhydrazino)4,5,4,5'd1benzothiaearbocyanine iodide (0.080) 16,9 1,9 .06 ((10 dye (m) (0.080) with dye (k) (0.030) 53.5 1.7 07 7 {(0) 9-(-zetyl-phenylhydrazmo) -3,3d.iethyl4,5,4',5dibenzothiacarbocyanine iodide 7.35 1. 9 .05 (p) dye (0) (0.080) with dye (k) (0.030) y 13.7 2.2 .06 )(q) 3,3diethyl-Q-hydroxamino-4,5,4,5dibenz0thiacarbocyamne iodide (0.080) 19.5 2,0 .07 8 \(r) dye (q) (0.080) with dye (k) (0.030) 53.5 1.8 -07 9 {(s) 3,3-dimetbyl-9-N-methylan1ino-4,5,425 dibenzothiaearbocyanine iodide (0.080) 53. 5 2. 3 .07 ((t) dye (s) (0.080) with dye (k) (0.030). l 82.5 1.8 .06

1' (u.) Q-N-ethylanilino-3,3dimethyl4,5,4,5'dibenzothiacarbocyanme iodide (0.080) 57. 0 2.1 .05 10 ((1,) dye (u) (0.080) with aye (k) (0030)-. 58.5 2.0 .06 l {(w) 3,3'diethyl9(i-piperidyl)-4,5,4,5-dibenzothiecarbocyaniue iodide .05 l (x) dye (w) (0.080) with dye (k) (0.030) 5.6 1.2 .06 12 {(y) dye (a) (0.08 9.7 2.7 .05 (z) dye (a) (0.080) With dye (k) (0.030) a 35.0 2.2 .06 13 {(a 3,3di.methyl9-N-methylanilinothiacarbocyanne iodide (0.080) 19. 5 2. 7 .05 (b) dye (a) (0.080) with dye (k) (0.030) 45.5 2.2 .06 14 {(c) 3,3-diethyi-Q-N-methyianilinocarbocyanne iodide (0.080) 2.95 0.85 .05 (d) dye (c) (0.080) with dye (k) (0.030) 8.85 2.6 .06 15 {(e') 5ch10r0-3,3dimethyl-Q-Nmethylanilinocarbocyanine iodide (0.080) 6.15 1. 5 .05 (f) dye (e) (0.080) With dye (k) (0.030) 30.0 2.2 .06 (g) dye (s) (0.080) 46.5 2.7 .06 16 (h) dye (b) (0.080) (1" dye (s) (0.080) with dye (b) 111. 0 2.3 07 (j') 5[(l-ethyl-2(1H)-B-naphthothiazolylidene) (l-methyl-2(1H)--naphthothiazolylidene) 19. 0 3.8 06 17 isopropylidene]-1,3di(,B-methoxyethyl) barbituric acid (0.080).

(k) dye (s) (0.080) with dye (j)' (0.030) 114. 0 2.3 .05 (l') 5-[(1ethy12(1H) --naphthothiazolylidene) (1 methyl-2(1H) --naphthoselenazolyli- 21.5 3.4 .07 18 dene)isopropyidene]-1,3-di(methoxyethyl)barbituric acid (0.080).

(m) dye (s) (0.080) with dye (l) (0.030) 4. 2. 5 .06 (n) 5-[(1-ethyl-2(1IE[)-B-naphthothiazolylidene)(1methyl-2(1H)-naphthothiazo1ylidene) .07 19 isopropylidene]-l-n-heptyl-S-phenylbarbituric acid (0.080).

(0') dye (s) (0.080) with dye (n) (0.030) 90. 5 2.4 .06 {(p) 5-[(di(le)thyl2(1H)--naphthothiazoiylidene)isopropylidene]1nheptylbarbituric acid 07 20 0.080

(q) dye (s) (0.080) with dye (p') (0.030) v. 102.0 2.6 .07 (r) 1,3 -dicyclohexyl5[di(l ethyl- 2(H) -naphthoth1azolylidene)isopropylidene]barbi- 05 21 turic acid (0.08

(3') dye (s) (0.080) with dye (r) (0.030). 58. 5 2.7 .06 (t) dye (s) (0.080). 25.5 1.65 .05 22 (u') 4-di(1-thy52GH)--naphthothiazolylidene)isopropylidene13phenyl5(4H)-isoxezo 5,1 1.56 .05

one 0.08

(11') dye (s) (0.080) with dye (t) (0.030) 37.0 1.63 .06 '23 {(w) 2[di(1-ethyl-2(1E[)-5-naphthothiazolylidene)isopropylidenel1,3-1ndandione (0.080).- 04 (I') dye (s) (0.080) with dye (w') (0.030) 31-5 L48 -06 with 9 N ethylanilino 3,3 dimethyl 4,5,4',5 di benzothiacarbocyauine iodide and curve D represents the sensitivity of the same emulsion containing 9 N ethylanilino 3,3' dimethyl 4,5,4,5' dibenzothia carbocyanine iodide and 5 [di(1 ethyl 2(1H) naphthothiazolylidene)isopropylidene] 1,3 di( methoxyethyl)barbituric acid. The sensitometric measurements for these emulsions are given in Example 10 of the above table.

In Figure 3 curve E represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 4 [di(l ethyl 2(11-1) naphthothiazolylidene)isopropylidene] 3 phenyl 5(4H) isoxazolone and curve F represents the sensitivity of the same emulsion containing 3,3'V dimethyl'- 9 N methyl anilino 4,5,'4,5' dibenzothiacarbocyanine iodide and 4 [di(l ethyl 2(1H) naphthothiazolylidene) isopropylidene] 3 phenyl 5(4H) isoxazolone. The sensitometric measurements for these emulsions are given inExample 22 above.

, My invention is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g.' gelatine-silver-chloride, chlorobromide, chloroiodide, -chlorobromiodide, -bromide and -bromiodide developing-out emulsions. While the results in the'above` tables were obtained using gelatino-silverbromiodide' emulsions, excellent results have also been obtained,V using gelatino-silver-chlorobromide emulsions.

Emulsions which form the latent image mostly inside the silver halide grains, such as the emulsions set forth in U. S. Patent 2,456,956, dated December V21, 1948, can also beemployedA in practicing my invention.

The emulsionsprepared in accordance with my invention can be coated in the usual manner on' any suitable support, e. g., glass, cellulose nitrate film, cellulose acetate film, polyvinylacetal resin-film, paper or metal.

Photographic silver halide emulsions, such as those listed above, containing the supersensitizing combinations of my invention can also contain such addenda as chemical sensitizers, Ve.v g., sulfur sensitizers (e. g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.vg., potassium chloroaurate, auric trichloride, etc.) (see U. S. Patents 2,540,085, 2,597,856 and 2,597,915), various palladium compounds, such as palladium chloride (U. S. 2,540,086), potassium aromi@ chloropalladate (U. S. 2,598,079), etc., orY mixtures of l such sensitizers; antifoggants,E such as ammonium chloroplatinate (U. $12,566,245); ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, ,nitrobenzimidazoles 5-nitroindazo1e, benzidine, mercaptans, etc. (see Mees,

The Theory of the Photographic Process, Macmillan Pub., page 460), lor mixtures thereof;v hardeners, Vsuch as formaldehyde (U. S. 1,763,533), chrome alum (U. S.

1,763,533), glyoxal (U. S. 11,870,354), dibromacrolenY (Br. 406,750), etc.; color couplers, such as those described in U. S. Patent 2,423,730, Spenceand Carroll U. S. Patent 2,640,776, issued June 2, 1,953, etc.; or mixtures of such. addenda. Dispersing agents for color Dy'e': M. P., fol (C') 112-4 (6') 135-7 dec.

1 Previous softening.

What I claim as my invention and desire secured by Letters Patent of the United States is:

1. A photographic silver halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented bythe following general formula:

//Z\` l/Zl\` wherein R and R1 each'represents an alkyl group, R represents an amino group, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected-from the group consisting of those of the benzothiazole series 4and those of the naphthothiazole series, and at least one un-ionized Ydye selected from those represented bythe following general formula:

wherein'Rg and R4 each represents an alkyl group, Zi

-represents themen-metallic atoms necessary to complete `-a= heterocyclic nucleus selected from the group consisting Vfrom the group consisting of those of the naphthothia'zole series and those of the naphthoselenazole seresandvQ represents the non-metallic atoms necessary to complete couplers, such as those set forth in U. S.-Patents2,322,027 and 2,304,940, can also be employed in the above-de Y scribed emulsions.

In the above table it will be noted that in certain-examples the amounts of dyes used in the supersensitizing each dye alone. Actually, supersensitization occurs ac-m cording to my -invention when the combinanon ofHdyejsH As noted above, many of the dyes selected from, thosev represented by Formula I can advantageously be prepared as described in the copending `application Serial No.

437,110 of Leslie G.` S. Brooker and Frank L. White.'

The dyes of Formula I wherein R0 is hydrogen and R2 Thus in-some instances, the amount of dye, l

combinations do not correspond to the amounts used with 'Y a nucleus selected from the group consisting of those of the indandione serles, those of the barbituric acid series,

those of the 2-thiobarbituric acid series, Vand those of the isoxazolone series.

2. A photographlc gelatino-silver-hahde emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by theV 'wherein Rand Ri eachrepresents an alkyl groupof the formula C11H2n+1 wherein n represents a positive integer of from l to 2, R represents an amino group, X-represents an acid radical, and Z 'and YZ1 each represents the is hydroxyl or arylhydrazino, or wherein R0 Yis alkyl andW R2 is aryl, can be prepared according Vto the method described in Belgian Patent 507,761, using hydroxylamine, an arylhydrazine, or an alkylarylamine (e. g.

N-methylaniline)`together with the appropriatechlorm.

propenyl heterocyclic compound. See also Ilford British Patent 684,650, published December 24, 1952.- Identifyin'g .data 'for a number of the' dyes (letters correspond to dyeused in above table) thus prepared are given below. k

non-metallic atoms necessary to complete a heterocyclic v nucleus selected from the group consisting of those of ,the'benzothiazole series and those of thenaph'tho/thiazhole series, and at least one un-ionized dye selected from those represented by the following general formula:

ing of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the nonmetallic atoms necessary to complete a nucleus selected from the group consisting of those of the indandone series, Vthose of the barbituric acid series,r those of the V9 Z-thiObarbituric acid series, and those of the soxazolone series.

3. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHzn-H wherein n represents a positive integer of from l to 2, R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group of the formula CdH2d+1 wherein d represents a positive integer of from l to 8, a hydroxyl group, a monocyclic arylhydrazino group, and an aromatic group containing from 6 to 10 carbon atoms, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series and those of the naphthothiazole series, and at least one un-ionized dye selected from those represented by the following general formula:

wherein R3 and VR4 each .represents an alkyl group of the formula CmH2m+i wherein m represents'a positive integer of from 1 to 2, Zzrepresents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the naphthothiazole series, those of the benzoselenazole series, those of the naphthoselenazole series, and those of the naphthoxazole series, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the non-metallic atoms necessaryvto complete a nucleus selected from the group consisting of those of the indandione series, those of the barbituric acid series, those of the Z-thio- `barbituric acid series, and those of the isoxazoloneseries.

4. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

N-Rg

. Il awherein R and R1 each represents an alkyl group of the formula CnHzn-H wherein n represents a'positive integer of from 1 to 2, Rn represent a carboxylic. acyl group containing from 2 to 8 carbon atoms, R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group of the formula CaH2d+1 wherein d is a positive integer of from l to 8, a monocyclic arylhydrazino group, and an aromatic group containing .from 6 to l0 carbon atoms, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series and those of the naphthothiazole series, and at least one un-ionized dye selected from those represented `by the following general formula: l

t com@ wherein Ik: and R4 each represents an alkyl group of the ormula CmHzm'H wherein m represents a positive integer of from 1 to 2, Zz represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those ofthe naphthothiazole series, those of the benzoselenazole series, those of the naphthaoselenazole series, andV those of the naphthoxazole series, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the nonmetallic atoms necessary to complete a nucleus selected from the group consisting of those of the indandione series, those of the barbituric acid series, those of the 2thiobarbituric acid series, and those of the isoxazolone series.

5. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

cal, and Z and Z1 each represents the non-metallic atoms\ necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series and those of the naphthothiazole series, and at least one un-ionized dye selected from those represented by the following general formula:

wherein R3 and R4 each represents an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 2, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected 'from the group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of those of the barbituric acid series, those of the Z-thiobarbituric acid series, vthose of the indandione series, and those of the isoxazolone series.

Y 6. A photographic gelatino-silver-halide emulsion sen- 'sitized with a supersensitizing combination of at least one carbocynine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnH2n+1 wherein n represents a positive integer of from 1 to 2, Ro represents a carboxylic acyl group containg fromt2 to 8 carbon atoms, 'R2 represents 4a member selected from the group consisting of a hydrogen atom, an alkyl group of the formula CdHztH-i wherein d is a positive integer of from l to 8, a monocyclic arylhydrazino group, and an aromatic group containing from 6 to 10 carbon atoms, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series and those, of the naphthothiazole series, .and at by the following general formula:

wherein Rs and R4 each represents an alkyl group ofthe formula CmHzm'H wherein m represents apositive inte ger of from 1 to 2, Z3 represents the lnon-metallic atoms necessary` to complete a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole series and those of the naphthoselenazoleseries, and Q represents the non-metallic atoms necessaryto complete a nucleus selected from the group consisting of those of the barbituric acid series, those of the Z-thiobarbituric acid series,; thofse of' thegindandione 'series,;and those of the isoxazolone series. f

7. A photographic gelatino-silver-bromiodide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula: A l/Z\ IZA" Y represented by the following general formula:

@H-o9 A wherein R3 and R4 each represents an alkyl `group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 2, Z2` represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected t from the group consisting of those of the benzothiazole series, those of the naphthothiazole series,A those of the benzoselenazole series, those of the naphthoselenazole series, and thoseof the naphthoxazole series,V Z3 represents the non-metallic atoms necessarytocompletea heterocyclic nucleus' selected from the.group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents` the nonmetallic atoms necessary to completea nucleus selected from the group consisting of those of thendandione series, those of the barbituric acid seriesl those gf the ...Z-thiobarbituricacid series, and those of the isoxazolone serles. f I Y 8. A photographic gelatino-silver-halid emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from Vthoserepresented by the followinggeneral formula:

Il R...

e-.p wherein R and-R1 each represents an alkyl group of 'the l2 one`un-ionized Bye' selected fromy those represented by the following general formula:

Y .Y dll- X709 wherein R3 and R4 each represents an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of kfromv 1 to 2, Z2 represents the'non-rnetallicatorns necessary'dtofcomplete a heterocyclic .nucleus selected from the group consisting of those of the benzothiazole series, those of the naphthothiazole series, 'those' Vof the Vbenzoselenazole' series, those Vof the naphthoselenazole series, and those of the naphthoxazole series, Z3 Yrepre-y sents the non-metallic atoms necessary to completea heterocyclicnucleus selected from lthe group consisting of those of. the naphthothiazole series and those'of the naphthoselenazole series, ran'dfQ represents the vnoni'netallic atoms necessary to complete a nucleus' selected from/the group consisting of those of the indandio'ne series, those of therbarbituric acid series, those of .the 2-th`iobarbituric acid series,v and those of the isoxazolone series.

9. A photographic gelatinosilverhalide emulsion sensitized with a 'supersensitizing combination of at least one carbocyanine dye'sele'cted from thoserepresented by the following lgeneral formula: t

.form-ula CnHnH wherein n represents a positive integer of from 1 to 2, Ro representsran alkyl group of the formula CaH2d+1 wherein d represents a positive integer of from 1 to 2, Rzrepresents a mononuclear aromatic` .group of the benzene series, X represents an acid radical,and Z represents the non-metallick atoms necessary to'complete 'Yavheterocyclic nucleus selected from the group consisting of those of the benzothiazole series.

andY those of the naphthothiazole series, and at least one un-ionized dye vselected from those represented byv the f ollowing general. formula:

'wherein R3 and R4 each `represents an alkyl group of the formula. CmHzm-t-'r wherein m represents a positive inte- L'ger' of from 1 to 2, Zarepresents the non-metallic atoms necessary to complete `a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole vseries and those of the naphthoselenazole series, and Q v'represents the non-metallic atoms necessary to complete -a nucleus selected from the group consisting of those of the barbituric acid series, those ofthe 2-thiobarbituric acid series, those of the indandione series, and those of the isoxazolone series.

10. VA photographic .gelatine-silver-halide emulsionsensitized witha .supersensitizing combination of at leastv la" p i N-Rx wherein Rand R1! .leach vrepresentsran alkyl .group ofthe 13 formula CnHn-i-i wherein n represents a positive integer of from l to 2, Rn represents an alkyl group of the formula Cdl-1254.1 wherein d represents a positive integer of from l to 2, R2 represents a mononuclear aromatic group of the benzene series, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the naphthothiazole series, and at least one un-ionized dye selected from those represented by the following wherein R3 and R4 each represents an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from l to 2, Z2 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the naphthothiazole series, those of the benzoselenazole series, those of the naphthoselenazole series, and those of the naphthoxazole series, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the naphhothiazole series and those of the naphthoselenazole series, and Q represents the nonmetallic atoms necessary to complete a nucleus selected from the group consisting of those of the indandione series, those of the barbituric acid series, those of the 2-thiobarbituric acid series, and those of the isoxazolone series.

1l. A'photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHan+1 wherein n represents a positive integer of from l to 2, Rn represents an alkyl group of the formula CdHzd-i-r wherein d represents a positive integer of from l to 2, R2 represents a mononuclear aromatic group of the benzene series, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the naphthothiazole series, and at least one un-ionized dye selected from those represented by the following general formula:

IZx`s` =ono=on rag-at wherein R and R1 each represents an alkyl group of the formula Cal-Izmir wherein n represents apositive integer of from 1 to 2, Rn represents a carboxylic acyl group containing from 2 to 8 carbon atoms, R2 represents a mononuclear aromatic group of the benzene series, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one un-ionized dye selected from those represented by the following general formula:

wherein R3 and R4 each represents an alkyl group of the formula CmHzm+1 wherein m represents a positive integer of from l to 2, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of those of the barbituric acid series, those of the 2-thiobarbituric acid series, those of the indandione series, and those of the isoxazolone series.

13. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHzni-i wherein n represents a positive integer of from 1 to 2, R0 represents a carboxylic acyl group containing from 2 to 8 carbon atoms, Rz represents a mononuclear aromatic group of the benzene series, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothazole series, and at least one un-ionized dye selected from those represented by the following general formula:

wherein R3 and R4 each represents an alkyl group of the formula CmHzm-H wherein m represents a positive integer of from 1 to 2, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the barbituric acid series.

14. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula Cal-12H1 wherein n represents a positive integer of from 1 to 2, R2 represents a mononuclear aromatic group of the benzene series, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the naphthothiazole series, and at least one 11n-ionized dye selected from vthose represented by the'tollowing'generl forwherein R3 and'R4 each represents an alkyl group of the formula GnH2m+1 wherein morepresents a positive integer of from 1 to 2, Z3 represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consistingofthose of the naphthothiazole series and those of the naphthoselenazole series, and Q represents the nonmetallic atoms necessary to complete a nucleus selected from the group consisting of those of the 'barbituric acid series, lthose of-the 2-thiobarbituric t acid series, thoseofthe indandione series, and those of the isoxazolone series. Y

15. A photographic gelatino-silver-halide emulsion sensitizedwith a supersensitizing combination of Yat least one carbocyanine dye selected from those represented by the following general formula:

wherein Rsand R4 each represents an alkyl group of the formula CmHzml-i wherein m represents a positive integer of from 1 to 2, Z3. represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those `of the naphthothiazole series and those of the naphthoselenazole series, and .Q represents the non-metallic atoms necessary lto complete a heterocyclic nucleus of the Vbarbituric acid series. 1

16. AV photographic gelatine-silver-halide emulsion sensitized with a supersensitizing combination of 3,3,di methyl-9-N-methylanilino4,5,4,5' dibenzothiacarbocya nine iodide and 1,3-diethyl-5- [di(1ethyl2(1H) --naphthothiazolylidene) isopropylidene] -barbituric acid.

17. A photographic gelatine-silver-halide emulsion sensitized with a supersensitizing combination of 3,3di methyl-9-N-methylanilino-4,5,4,5' dibenzothiacarbocyanine iodide and 5-[(1-ethyl-2(1H)naphthothiazolyl idene) (l methyl 2( 1H) --naphthothiazolylidene)isopropylidene] -1,3di(,8methoxyethyl)barbituric acid.

18. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination ofl 3,3dimeth` yl-9-N-methylanilino 4,5 ,4',5 dibenzothiacarbocyanine iodide and 5 l-ethyl-2(1H)--naphthothiazolylidene) 19. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of 9-(acetylp-phenetidino)-3,3'-dimethylthiacarbocyanine p-toluenesulfonate and 1,3-diethy1-5[di(1ethyl2(1H)-naph thothiazolylidene) isopropylidene] barbituric acid.

20. A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of 3,3di

methyl-v9-p-phenetidino-4,5 ,4,5 '-dibenzothjacarbocyanine chloride and 5-[di(1-ethyl-2(1H)naphthothiazolylf ideehsopropylidenel- 1,3 di( -methoxyethyl)barbituric aci i No'referencescited 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION SENSITIZED WITH A SUPERSENSITIZING COMBINATION OF AT LEAST ONE CARBOCYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 